TWI417348B - 1-phenoxy-2-propanol as a formulating aid for dyes - Google Patents

Abstract

The invention relates to an aqueous dye solution comprising a) 5 to 30% by weight of an anionic or cationic direct dye, b) 0.1 to 10% by weight of 1-phenoxy-2-propanol, c) 0 to 20% by weight of an inorganic or an organic acid, d) 0 to 20% by weight of further additives and e) water to complete to 100%, a process for the preparation of the solution and the use thereof for dyeing paper.

Description

1-phenoxy-2-propanol as a dyeing aid

The present invention relates to a storage stable concentrated aqueous solution of a direct dye (including an anionic dye and a cationic dye), a method of preparing the same, and use thereof for paper dyeing.

In recent years, the use of concentrated aqueous solutions of dyes has received increasing attention, particularly in the dyeing of papers, which have advantages when compared to dyes in powder form. Therefore, for example, the use of a solution can avoid the formation of dust, so that the user can avoid the problem of time consuming and often difficult to dissolve the dye powder in water. The use of concentrated solutions has also received attention due to the development of continuous dyeing processes in which it is readily possible to meter solutions directly into the pulp stream or at some suitable location during papermaking. However, even at relatively low temperatures, such solutions should be ecologically and toxicologically acceptable, storage stable, in a concentrated form, and easy to pump.

In recent years, EP 1,235,881 B1 has revealed a method for solving this problem, which is found to be obtained by adding an aqueous solution of a concentrated water-soluble anionic dye by adding up to 4% of benzyl alcohol, although it is not disclosed. The storage stability is defined, but the solutions are stable for storage and, although not disclosed by the data, can also exhibit desirable flow characteristics. In addition, this document also describes various prior means, such as by the addition of urea, urea/N-methylpyrrolidone/benzyl alcohol mixture, alcohols including glycols and glycol ethers, and other organic solvents. Providing an aqueous dye solution with storage stability and solving its shortcomings in application.

Although benzyl alcohol appears to be an optional additive for formulating aqueous anionic dye formulations with storage stability, a significant disadvantage is that even with relatively small amounts, there is an undesired benzyl alcohol odor.

Surprisingly, it has now been found that the use of 1-phenoxy-2-propanol as a formulation aid provides an odorless formulation for both anionic and cationic direct dyes with long-term storage stability and flow characteristics. It is better than the formulation of benzyl alcohol disclosed in the prior art.

Accordingly, the present invention relates to an aqueous dye solution comprising: (a) 5 to 30% by weight, preferably 10 to 25% by weight of an anionic or cationic direct dye; (b) 0.1 to 10% by weight, It is preferably 0.5 to 5% by weight, and most preferably 0.5 to 3% by weight of 1-phenoxy-2-propanol; (c) 0 to 20% by weight of an inorganic or organic acid; (d) 0 to 20 % by weight of other additives; and (e) the balance being water to achieve 100% by weight.

If the solution of the present invention is an anionic dye solution, such direct dyes are preferably selected from dyes containing at least one sulfonic acid and/or carboxylic acid group and are derived from dyes of the following classes: no metal or metal monocouple Nitrogen, diazo, and polyazo dyes, pyrazolone, 9-oxosulfur (thioxanthone), , stilbene, formazan, guanidine, nitro, methine, triphenylmethane, Xanthone, naphthoquinone, styryl, azostyrene, naphthoperinone, quinophthalone, and anthraquinone dye.

A representative example series of anionic direct dyes is given in "Colour Index International", 4th edition online (website: http:/www.colour-index.org), and can be selected from: CI Direct Yellow 1-177, CI Direct Orange 1-122, CI Direct Red 1-277, CI Direct Purple 1-108, and CI Direct Blue 1-313.

If the solution of the invention is a cationic dye solution, then the cationic direct dyes are basic dyes. These so-called basic dyes are selected from the following categories: acridine, hydrazine, , imine, azostyrene, mono-, di- and polyazo, benzimidazole, benzothiazole, cyanine, di- and triarylmethane, ketimine, methane and poly Methyl, naphtene styrene, nitro, ,two , anthracycline, quinoline, quinophthalone, thiophene Thiazole and (xanthene) derivative.

Representative examples of cationic direct dyes are listed in "International Dyestuff Index Numbers", 4th Edition Online (website: http:/www.colour-index.org), and may be selected from: CI Basic Yellow 1-108 , CI alkaline orange 1-69, CI alkaline red 1-118, CI alkaline violet 1-51, and CI alkaline blue 1-164.

The invention is particularly useful for solutions of specific dyes, such as CI Basic Yellow 99 and 106, CI Basic Red 111, CI Basic Blue 100 and 153, CI Direct Yellow 11, 50 and 84, CI Direct Orange 29 and 102, CI Direct Red 23, 80, 81, 239, 254 and 262, CI Direct Violet 9, 35 and 51, and CI Direct Blue 75, 86, 87, 199, 290 and 301.

If the composition of the present invention contains an organic or inorganic acid, the acid which is particularly suitable may be selected from, for example, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, glycolic acid, gluconic acid, methanesulfonic acid, lemon. Acid, succinic acid, lactic acid, glutamic acid, adipic acid, or mandelic acid. Although formic acid is preferred, any of these acids may be used alone or as an acid mixture.

Although the acid is added in the present invention as the case may be, the acid content is preferably between 1 and 20% by weight, preferably between 1 and 5% by weight based on the total weight of the composition. .

In addition to this, the dye solution according to the invention may contain other additives as component (d), such as water-soluble organic solubilizers, examples of which are urea, formamide, ε-caprolactam; sugars such as dextrin, Maltose, or lactose; carboxy cellulose, for example Xanthan, dimethylformamide, 1,2-diaminopropane, 2-(4-chamberylphenyl)-6-methylbenzothiazole 7-sulfonic acid, and salts thereof; Polyols such as ethylene glycol or glycerol; and among these, ε-caprolactam, and 2-(4-aminophenyl)-6-methylbenzothiazole 7- are preferred. Sulfonic acid, and its salts. Further additives which may be present in the solution according to the invention are, for example, hydrotropic agents, viscosity regulators, dispersants, bactericides, in particular fungicides and pH regulators.

As the "pH adjuster", an acid, a base or a buffer which is conventionally used for pH adjustment of a dye formulation, such as a mineral acid such as hydrochloric acid, sulfuric acid, or phosphoric acid; for example, having a carbon number of 1 to a low molecular weight aliphatic carboxylic acid of 6, such as formic acid, acetic acid, lactic acid, or citric acid; or a base such as an alkali metal hydroxide; or a carbonate; or an aliphatic low molecular weight amine, such as may be used to form The corresponding salt of the acid as described above, for example, ammonia, diethanolamine, triethanolamine, or N-methyldiethanolamine. As the "buffering agent", for example, monosodium or disodium phosphate, sodium acetate, or ammonium sulfate can be used.

Thus, the pH of the concentrated dye solution can be adjusted as needed, depending on the particular dye being considered. However, it is preferred that the pH of the solution is usually in the range of from 3 to 11. Therefore, in the case of a cationic dye, it is preferably in the range of from 4 to 6; however, in the case of an anionic dye, the pH is preferably between 6 and 8.

The aqueous solution preferably also contains conventional products which are generally used to protect against the deleterious effects of microorganisms, i.e., products which substantially inhibit the growth of microorganisms, or bactericides, particularly fungicides. These can be used at low concentrations, for example in the range from 0.01% to 1%, especially from 0.05% to 0.5%.

Although the addition of such additives to the composition of the present invention is optional, based on the total weight of the composition, the preferred content is between 1 and 20% by weight, most preferably between 1 and Between 10% by weight.

The solution of the present invention is preferably substantially free of other solvents, particularly alcohols other than 1-phenoxy-2-propanol, except for minor amounts of impurities and salts which may result in dye synthesis.

In another feature, the invention relates to a process for formulating a dye solution which comprises dyeing a component comprising water as described above, 1-phenoxy-2-propanol, and if desired ( The mixture of c) and (d) is stirred at a temperature between room temperature and 90 ° C, preferably between 30 ° C and 60 ° C; and, if necessary, filtered. The dye system can be used in the form of a corresponding dry dye, as in the blended commercial grade form, or preferably as a wet or dry filter cake which has been previously purified by microfiltration or ultrafiltration, or Use as a solution.

The anionic dye is preferably present in the form of an easily water-soluble salt. Thus, suitable salts are alkali metal salts such as lithium, potassium or especially sodium or ammonium salts, mono-, di-, tri- or tetra-C ₁ -C ₄ alkyl ammonium salts, or C ₂ to C ₄ hydroxyalkyl ammonium salts, or mixtures thereof.

Similar to this, in the case of a cationic dye, the counter ion should be such that it ensures sufficient water solubility. Preferred salts in this case are, for example, halides, especially chlorides, sulphates, methyl sulphates, and especially low-carbon aliphatic carboxylic acid esters such as formate, acetate and lactic acid. Esters.

The formulations of the present invention are suitable for dyeing natural or synthetic materials, particularly cellulosic materials in any desired color. In particular, the formula is suitable for dyeing paper and board.

Thus, in another feature, the invention relates to the use of a solution for the dyeing of paper, which is treated with a liquid composition as defined above. If necessary, the diluted solution can be used for dyeing paper or paperboard, so these materials can be dyed in, for example, pulp, applied by brushing or dipping, or by coating or spraying on the surface of the paper. The paper or paperboard which has been dyed with the liquid composition of the present invention constitutes another feature of the present invention, or for use in a continuous dyeing method or the like.

The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention, in which "parts" and "percentage" are by weight unless otherwise specifically mentioned.

[Example 1]

Mixing a mixture of 100 parts of ε-caprolactam, 30 parts of 1-phenoxy-2-propanol, 18 parts of formic acid, and 270 parts of water and heating to 40 ° C, then adding 600 parts of a wet cake containing 37.5% of the dye CI basic blue 100 as shown in the formula (101) preliminarily precipitated at a pH of 9.0 and washed to an inorganic salt-free layer: CuPC{[SO ₂ NH( CH ₃ ) ₂ 〕 _{2 - 3} SO ₃ H} _{1 - 2} (101), wherein PC is representative of anthraquinone. After stirring at 60 ° C for 2 hours, the mixture was cooled and filtered to obtain a dye containing 22.5% of the formula (101), 10% of ε-caprolactam, 1.8% of formic acid, and 3 A solution of % 1-phenoxy-2-propanol.

The solution showed a dynamic viscosity of 300 mPas (at 5 ° C), was easily diluted with water, and was stable for storage over a period of 6 months at temperatures between -10 ° C and 50 ° C.

A stable formulation similar to this can be obtained by using various amounts of 1-phenoxy-2-propanol in the range of from 1 to 5%, whereby the dynamic viscosity of the solution obtained depends on the use. Depending on the amount of alcohol, it ranges from 1,500 to 200 mPas.

In addition, a stable formulation similar to that obtained contains between 1 and 5% formic acid instead of 1.8% formic acid, depending on the amount of acid added, the pH of the solution. The change is between 3 and 6.

Stable formulations are also available from salt-containing dye cakes, whereby the viscosity of the solution is only slightly increased.

[Comparative Examples 2 to 6]

The dynamic viscosity of the obtained solution was determined by carrying out the procedure as described in Example 1, except that 30 parts of 1-phenoxy-2-propanol was substituted with 30 parts of the additive shown in Table 1. The results are summarized in Table 1 below.

It is apparent from the results shown above that the viscosity of these solutions is substantially higher than the viscosity of the solution of Example 1.

[Example 7]

A salt-free concentrate of CI Direct Orange 102 dye as shown in formula (102) obtained directly from synthesis and filtration:

It was treated with 1-phenoxy-2-propanol and diluted with water to obtain a compound containing 1% of 1-phenoxy-2-propanol and 14% of the formula (102).

The solution obtained showed a dynamic viscosity of 50 mPas (at 25 ° C) and was shown to be stored at temperatures between -10 ° C and 50 ° C for a period of more than 6 months without deposition.

[Comparative Examples 8 to 18]

By carrying out the procedure as described in Example 7, but replacing 1-phenoxy-2-propanol with the same amount of additives as shown in Table 2, the obtained solution was measured for its dynamic viscosity and The results are summarized in Table 2 below.

It is apparent from the results shown above that the viscosity of these solutions is substantially higher than the viscosity of the solution of Example 7.

Claims (11)

An aqueous dye solution comprising: (a) 10 to 25% by weight of an anionic or cationic direct dye, (b) 0.1 to 5% by weight of 1-phenoxy-2-propanol, (c) 0 Up to 20% by weight of inorganic or organic acid, (d) 0 to 20% by weight of other additives, and (e) the balance being water to reach 100% by weight. The aqueous dye solution of claim 1, wherein the anionic direct dye contains at least one dye of a sulfonic acid and/or a carboxylic acid group, and is derived from a metal or metal monoazo, diazo, or Polyazo dyes, pyrazolone dyes, 9-oxosulfur (thioxanthone) dye, Dyes, stilbene dyes, formazan dyes, anthraquinone dyes, nitro dyes, methine dyes, triphenylmethane dyes, Xanthone dye, naphthazarine dye, styryl dye, azostyrene dye, naphthoperinone dye, quinophthalone dye or anthraquinone dye. The aqueous dye solution according to claim 1, wherein the cationic direct dye is a basic dye selected from the group consisting of an acridine basic dye, an alkaline dye, Basic dyes, azomethine basic dyes, azostyrene basic dyes, mono-, di- and polyazo basic dyes, benzimidazole basic dyes, benzothiazole basic dyes , cyanine basic dyes, di- and triarylmethane basic dyes, ketimine basic dyes, methane and polymethine basic dyes, naphthacene styrene basic dyes, nitro basic dyes , Basic dye, two Basic dye, anthraquinone basic dye, quinoline basic dye, quinophthalone basic dye, thiophene Basic dyes, thiazole basic dyes and A group of derived basic dyes. The aqueous dye solution of claim 1, wherein the aqueous dye solution is substantially free of an alcohol solvent other than 1-phenoxy-2-propanol. The aqueous dye solution according to claim 1, wherein the other additive is selected from the group consisting of a water-soluble organic solubilizer, a hydrotropic agent, a viscosity modifier, a dispersant, a bactericide, and a pH adjuster. Group. The aqueous dye solution according to claim 5, wherein the water-soluble organic solubilizing agent is selected from the group consisting of urea, formamide, ε-caprolactam, saccharide, carboxy cellulose, dimethylformamide, 1 , 2-diaminopropane, 2-(4-aminophenyl)-6-methylbenzothiazole 7-sulfonic acid and salts thereof; and a group of polyols. The aqueous dye solution of claim 2, wherein the anionic direct dye is derived from a monoazo, diazo, polyazo or anthrain dye. The aqueous dye solution according to claim 3, wherein the anionic direct dye is selected from the group consisting of mono-, di- and polyazo basic dyes and anthraquinone basic dyes. A method for preparing an aqueous dye solution according to claim 1, which comprises stirring an anionic or cationic direct dye with water, 1-phenoxy-2-propanol, and 0 to 20% by weight of inorganic Or a mixture of an organic acid and 0 to 20% by weight of other additives. A method of dyeing paper, paperboard or pulp, which comprises applying an aqueous dye solution as described in claim 1 of the patent application to the paper, paperboard or pulp. A paper dyed with an aqueous dye solution as described in claim 1 of the patent application.